Apparatus for carrying out chemical reactions in the presence of finely-divided powder



l June 17, 1947. B, E RQETHELI 2,422,501

APPARATUS FOR CARRYING OUT CHEMICAL REACTIONS IN THE PRESENCE 0F FINELY-DIVIDED POWDER Filed Dec. 8,f 1944 2 Sheets-Sheet 1 FIG-J /23 "l r1 f1 r' ll Il 1I Il I l I l I Il ILl L==l 29 lcani/.121?.

1 z QUE/VCH l 55 l l i .SOL/D3 LJ 5.4752 fi-SEPARATOR 'cARz/Ez GAS June 17, 1947. B. E. ROETHELI 2,422,501

'- APPARATUS FOR CARRYING OUT CHEMICAL REACTIONS IN THE PRESENCE OFlFINELY-DVIDED POWDER Patented June l?, 1947 UNITED STAT-Es PATENT omer:

APPARATUS FOB CARRYING OU'II.` CHEMI- V(JAL REACTIONS IN THE PRESENCE( F FINELY-DIVIDED POWDER ration oi Delaware Application December s. 1944, serial Nats-1.271

(ci. zs-zsz) lclalma.

l This invention relates to carrying out chemical reactions in the presence of iinely-divided solids,A

and pertains more particularly to processes requiring high temperatures and extremely short reaction times.

While the invention in some of its broader phases has a more general application, it is particularly adapted for the high temperature crack` ing 0f hydrocarbon gases and vapors to form acetylene, ethylene, and other low-molecular weight oletlnic hydrocarbons and hydrogen.

`It has previously been known that acetylene could be formed from hydrocarbon vapors by exposing the vapors to extremely high tempera-` tures, such as of the order of from 1800 F. to

2600 F., for extremely short reaction periods.

It the vapors are left exposed to the'high temperatures for prolonged periods, however, undesirable secondary reactions take place.

One of the practical diiliculties which thus far has not been successfully overcome is getting heat into and out of the vapors in an extremely short period of time. One method heretofore employed involved passing the hydrocarbon vapors through an electric arc and immediately' quenching the vapors with cooledoil or gas. While this method permits rapid heating and cooling, it has thus far proven too expensive to compete successfulLv with the calcium carbide process for the production of acetylene.

Other proposals for producing acetylene from hydrocarbon vapors involved passing the vapors through radiant tubes or in contact with highly proved process for rapidly heating and rapidly cooling vapors orgaseous reactants.

Another object is to provide an improved apparatus for carrying out chemical reactions requiring high temperatures and short reaction times.

Another more specific object is to provide an improved method and apparatus for rapidly cooling gaseous reaction products.

Other speciilc objects and advantages of the invention will be apparent from the detailed de- 2 scription hereinafter in which reference will be made to the accompanying drawings wherein- Fig. 1 is a partly schematic and partly diagrammatic illustration of an apparatus forming a part of the present invention and capable of carrying out the method phases of the invention; and

Fig. 2 is a similar view showing a modiiication of a method of quenching or cooling gaseous reaction products.

In accordance with the present invention, the gases to be reacted are introducedinto the bottom of a reaction zone which is maintained at the desiredv high reaction temperature by the continuous introduction of a highly heated powder..

'I'he reaction products are quickly withdrawn from the reaction zone together with the powder and immediately discharged into a cyclone separator in which the swirling motion of the gases and powder around the outer shell of the cyclone effects rapid separation oi the bulk of the powder from the reactant gases. The gases are withdrawn from the cyclone through a central tube and the separated powder -discharges into a hopper forming the bottom section of the cyclone separator.

In accordance with one phase of the present invention,v a quenchingv medium in the form of a solid, liquid or gas is injected into the central duct of the cyclone separator so that the gaseous reactants immediately following separation of the bulk of the powder are rapidly cooled to a temperature which will avoid or reduce undesirable secondary reactions. By quenching the reactant gases immediately following the primary separation of the powder used tor supplying the heat, the powder may be circulated with a minimum loss of heat and less quenching medium will be required.

According to another modication of theinvention, as illustrated in Fig. 2, the reaction products following separation from the powder are immediately quenched by injecting a cooled powder, and the resulting mixture'may or may not thereafter be passed through further cooling elements.

The reactant gases after being allowed to contact with the quenching medium may discharge into a secondary separator wherein further separation of entrained powder from the reactant gases may be effected. In event the finely-divided powder comprises part or all of the quenching medium, the secondary separator may be used ior-eilecting separation of the quenching powder.

In other cases where a gaseous or liquid l quenching medium is sive, the secondary separator-may be omitted. The v reaction products following the initialv quenching treatment may be passed through iurther cooling zones wherein they are sublectedto additional cooling preparatory to final separation and purincation of the desired reaction products.

The hot powder separated from the"-gaseous reaction products is passed through a heater wherein it is heated to a temperature suiiieient to heat the feed vapors tothe desired reaction employed and the powder employed as a heat carrier is relatively inexpentemperature and also to supply the heat of reaclarge quantities of powder. In order to restore the pressure lost during circulation, a standpipe is placed either in the lineior returning the powder from the reaction zone to the heating zone or in the line foireturning the powder lfrom the heating zone to the reaction zone, or a separate standpipe -may be provided in each line.

These standpipes are adapted to contain a col-' vumn of powder of a height suicient to restore the pressure lost in other sections of the circulating system, such as in the heating zone and reaction zone. In order rto generate' a maximum pressure at the base of the column and avoid packing and bridging oi the powder within the column, it is important to'maintain the powder within the column in a uid state. This can be done by maintaining a small amount of an aerat- .ing or iuidizing gas in admixture withthe powder within the column. Itis known that powders may be made to behave in many respects as a v liquid by maintaining a small amount of a gas in intimate mixture therewith. When maintained in a iiuidized state by the presence of a -small amount vof gas, a hydrostatic pressure may be generated at the base of the column. The use of standpipes for restoring pressure on the catalysts provides a lsimple and inexpensive means for circulating relatively large quantities of powder through the cracking and heating zones.

Control valves for regulating the flow of powder through the heating and reaction zones are preferably located in the cooler sections of the equipment, such as in the lines leading from the reaction zone into the heating zone.

In order to maintain a seal between the heating zone and the reaction zone and thus prevent the feed vapors from leaking back through the powder transfer line into the heating zonel the transfer line may be provided with vone or more iixed orices through which the powder` must pass. Steam or other inertl gas may be introduced below the orices or between the oriiices, in event two are employed. so as to further insure the maintenance of a proper seal between the heating and reaction zones by maintaining powfder in the iluid state.

'I'he heating of the powder is preferably carried out in an enlarged zone through which a heating gas is passed upwardly at a regulated velocity to maintain the powder ina highly turbulent state. This insures that the powder passing to the reaction zone will be at substantially uniform temperature. In view of the high tem.. perature of the reaction, which, as previously mentioned, may be of the order of from 1800 F.

to 2600' F., all parts of the equipment of suiilclent diameter should be internally lagged with vvrefractories. Other portions of the equipment exposed to high temperature may be constructed of heatresisting alloys.

The powder used as the heat carrier may com,-

prise'any refractory material, such as brick dust, carborundum powder, -purii-led sand, silica gel. and powdered metals or alloys. The powder employed may be inert to the reaction carried out or, if desired, the powder may comprise or contain catalytic agents;

Having set forth the'general nature. and objects. the invention will now be described with reference to the drawings.

Referring to Fig. l, the reference character I0 designates a charge line through which the feed gas or vapors are introduced into the system. For illustrative purposes, the invention will be described as applied to the cracking of hydrocarbon gases or vapors to form acetylene and ethylene. i

The feed vapors or gases introduced through lineA I0 discharge into the bottom portion 'of a reactor II below agrid I2 through which the vapors are distributed over the 4full cross-sectional area of the reactor. The vapors passing through the grid I2 immediately contact a stream of highly heated powder which discharges into the reactor I I through a conduit I3. f The amount and temperature of the powder'. introduced into the reactor are suilicient to heat the gases or vapors to the desired .temperature and to supply the necessary heat for the reaction. The feed vapors prior to introduction into the reactor may be preheated to a temperature below decomposition temperature,` such as from 500 F. to l500 F., and the amount and temperature of the catalyst may be sufdcient to heat the vapors to a reaction temperatureasuch as from 1800 F. to 2600 F. The gases orvapors rising through the reactor Il carry the heated powder therewith and the mixture of powder andxreaction products is withdrawn from the upper end of the reactor throughV conduit I4 directly into a cyclone separator I5.

The size of the reactor II and the velocity of the gases or vapors passing therethrough are controlled so that the time of residence of the vapors or gases within the reaction zone is extremely short. This residence time may, for example. range between one-hundredth of a second to 2 seconds. The reaction products and powder discharge into the cyclone separator I5 in a tangential manner to set up a swirling motion in the outer section of the cyclone and thus throw the powder to the outer surface. The

powder so separated falls into the bottom 0f the temperature which will avoid or reduce unde'v The central duct v I6 may be provided with a throat I'I at thepoint sirable secondary reactions.

of discharge of the quenching medium to increase turbulence and improve mixing. The reactant vapors together with the quenching medium are removed from the cyclone separator I5 through a conduit I8 and pass into a quenching zone I s wherein the vapors are retained for a suilicient period to insure lowering the temper-f ature to the desired level. This temperature may, for example, be of the order of from 500 F. to l500 F., depending upon the nature of the products made. The reactant gases after passing through the quenching zone I9 may dis- Charge into a secondary cyclone separator 2I wherein any entrained powder not removed in the primary separator I5 may be further separated. The powder separated in the separator 2I is collected in the bottom portion thereof and the reactant gases together with the quenching medium are withdrawn through acentral duct 22. 'I'hese products may be passed through afurther heat exchanger 23 which may be an indirect heat exchanger, as shown. or a directheat exchanger for reducing the temperature of the products preparatory tofinal separation and puriilcation. Reaction products are removed from the heat exchanger 23 through line 30.

The powder separated from the main reactant stream in the initial cyclone I5 discharges into the top of a vertical conduit 24 which serves as a standpipe for restoring a part or all of. the pressure on the powder being circulated. If desired, a small amount of an aerating or iluidizing gas may be introduced into the conduit 24 at one or more spaced points through lines 25 and 28. 'I'he powder discharges from the base of the standpipe 24 through a control valve 21 into a stream of carrier gas passing through line 28 and is transferred into the bottom portion of a heater 29.

The powder separated from the reaction products under the conditions above described will normally contain a substantial amount of combustible deposits which may be burned in -the heater 29 to supply heat to the powder. The carrier gas in such case may comprise air.

The heating chamber 29 is preferably in the form of a vertical vessel having an inverted conical bottom into which the stream of powder and carrier gas discharges. A. grid plate 3I may be provided in the bottom portion of the vessel for distributing the powder and gas uniformly over .the full cross-sectional area of the heater. The velocit of the air stream rising through the heater 29 s preferably maintained sumciently low to cause primary separation of the powder from the air and form a relatively densebody of powder in the bottom portion of the heating vessel. Under properly controlled conditions a relatively dense," turbulent, iluid layer of powder may be maintained in the bottom portion of the heating vessel superimposed by a relatively dilute phase of gases containing entrained powder. This powder will be maintained in a highly turbulent state by the gases risingA therethrough. The combustion gases are withdrawn from the upper portion of the heating vessel 29 through an internal cyclone separator 32 wherein endischarges downwardly through the conduit 34.

into a conduit 3l which may comprise an 'extension of the conduit 34 located in the vessel 29. I! desired. a fuel gas maybe discharged into the conduit 35 through line 33 to supply' additional heat to the powder. This also acts as a iiuidizing gas. The conduitl 33 is preferably provided with spaced fixed orlces 31 and 33 between which a stream of steam or other sealing gas may be introduced through line 33. The conduit 35 discharges at the base into the conduit I3 which leads to the reaction chamber II. 'Ihe powder is heated in the heating vessel' 23 to a temperature substantially above the temperature maintained in the reactor II. and the rate of circulation of the powder through the heating and reaction zones is preferably maintained clone 2IV also discharges into the top of a vertical conduit 4I which forms a standpipe for restoring the pressure on the powder. To this end, an aerating gas may be introduced into the standpipe 4I at one or more spaced points through lines 42, 43 and 44. The powder discharges from the base of the standpipe 4I through a control valve 45 into a stream of carrier gas passing through line 45 and is introduced into the base of the heater 29.

Fig. 2 illustrates an alternate method of quenching the reaction products. The heating vessel and the reaction zone are oi' the same construction as that shown in Fig. l and like reference characters have been used Vfor designating. similar parts. In place of introducing a quenching medium into the central conduit of the cyclone separator I5, as shown in Fig. 1, the quenching is accomplished in Fig. 2 vby introducing a cool powder into the reactant stream.

Referring to Fig. 2, the hot, gaseous reaction products separated from the powder in the cyclone separator I5 are withdrawn through a conduit 5I into which a stream of cool powder is introduced from the base of a .vertical standpipe 52 at a controlled rate through valve 53. TheA amount and temperature of the powder introduced into the conduit 5I may be lsuillcient to quench the reaction products to a temperature suiilcient to avoid undesirable secondary reac-v tions, or the resulting mixture of cooled 'powder and gaseous reaction products may be passed upwardly through a cooling zone 54 wherein further cooling may be eiected, such as by' the injection of a vaporizable liquid through line 55. If desired, the cooling may be effected by providing cooling tubes in the cooling chamber 54.

`The cooled mixture oi gaseous reaction products and powder is withdrawn l:lfrom the cooling zone 54 through conduit 53 which discharges into a cyclone separator 51 wherein the cooledy pow-V der is separated-from the cooled reaction products. The gaseous reaction products may 4be withdrawn through conduit 33 and may be passed to additional coolers such as shown in Pig.,1 for reducing the temperature of the reactant gases preparatory to further separation and purication. The powder separated from the reactant gases in the cyclone J discharges into chamber includes a standpipe adapted to contain a column of powder or a height suillcient the top of the vertical standpipe 52 where it is ther cooling the powder introduced into the conduit Il. A uidizing gas may be introduced into the standpipe 52 at one or more points through line: 60, 8| and 62. A cooling fluid may be introduced into the jacket 59 surrounding the standpipe 52 through line 63 and removed through line 64. I n some cases the amount and temperature of the cooler powder introduced into the conduit 5I may be sufiicient to lower the temperature of the reaction products to the desired extent. In the latter case the cooling zone El and the introduction of the vaporizable liquid through line 55 may be omitted. In this event, the powder will be'subjected to the necessary cooling following separation of the powder from the cooled reaction gases.

In most cases it is preferable not to quench the products below the dew point of the vapors being quenched. In some cases suilicient condensation may be obtained to separate or scrub entrained powder from the reactanty gas.

Having set forth in detail the nature and objects of my invention and the preferred mode of operation, it will be understood that it is not -limited to the exact details illustrated and described, as other obvious modincations apparent to those skilled in the art.

What is desired to be protected Patent is:

1. An apparatus for processing gaseous mawill be by Letters terial at high temperatures for short reaction` periods comprising a vertical reaction chamber, a conduitl connected with one end of said chamber for introducing the gases to be reacted, means including a separate conduit for introducing a stream 'of hot powder into said reaction chamber, a third conduit in open communication with the end of said reaction chamber opposite said rst-named end for withdrawing a mixture of powder and gaseous reaction products from said chamber, means immediately adjacent the lastnamed. end of said chamber for separating powder from said gaseous reaction products, means for injecting a cooling medium into said gaseous reaction products immediately following separation of the powder therefrom, a separate heating chamber adapted to heat the powder to a temperature materially above the temperature maintained in said reaction cnamber, means for transferring powder separated from said gaseous reaction products to said heating chamber, said first-named separate conduit being in open communication with said heating chamber and adapted to eiect transfer of heated to restore pressure lost on the powder circulated throughsaid heating chamber and said reaction chamber, and means for maintaining the column of powder within said standpipe in a fluid state capable of generating a hydrostatic pressure at the base thereof.

3. The apparatus deined by claim 1 wherein the means for transferring the powder separated from said reaction products to said heating chamber comprises a standpipe adapted to contain a column of powder of a height suillcient to restore the pressure lost during circulation of the powder through'said heating and reaction chambers. means for maintaining the powder within said column in a free iiowing iluidized Y state capable of generating a hydrostatic prespowder from said heating chamber directly to Y sureat the base thereof and a valve at the base of said standpipe for controlling the rate of ilow of said powder through 'said heating and ref` action chambers.

4. An apparatus for processing gaseous materials at high temperatures for short reaction periods comprising a vertical reaction chamber,

a conduit connected with one end of said cham-f ber for introducing Igases to be reacted, a separate conduit connected to said chamberfor introducing highly heated powdertherein, a third conduit opposite said first-named conduit for withdrawing a mixture ofpowder and gaseous reaction products from said chamber, *means immediately adjacent said last-named end of said chamber for separating powder from said hot gaseous reaction products, means for immediately cooling said gaseous reaction products following the separation or the powder therefrom, a

heating chamber adapted to heat said powder l materially above 'the temperature maintained in said reaction chamber, said mst-named separate conduit being in open" communication with said heating zone and adapted to transfer the heated powder directly from said heating chamber to said reaction chamber, a plurality of restricted oriiices positioned within said separate conduit, means for introducing a sealing gas between said orifices to eiect a gaseous seal between said heating chamber and said reaction chamber, and means for passing powder separated from said gaseous reaction products to said heating zone whereby said powder may be continuously circulated through said heating and reaction chambers.

BRUNO E. ROETHELI.

RFRENCES CITED UNITED STATES PATENTS Number Name Date 2,259,487 Payne Oct. 21, 1941 2,300,152 Hemminger Oct. 27,. 1942 2,303,047 Hemminger Nov. 24, 1942 2,304,128 Thomas Dec. 8, 1942 2,331,433 Simpson et al Oct. 12, 1943 2,367,281 Johnson Jan. 16, 1945 2,341,193 Scheineman Feb. 8, 1944 2,362,621 Fahnestocl Nov.v 14, 1944` 2,366,805 Richker Jan. 9, 1945 2,373,358 Upham et al. Apr. 10, 1945 2,376,190 Roetheli et al. May 15,1945

of record in the 

